ES2199890T3 - ZWITTETIONIC SILOXANE POLYMERS AND IONICALLY FORMED RETICULATED POLYMERS FROM THE SAME. - Google Patents

Abstract

A method for preparing an ionically crosslinked composition of a consistency similar to a thickened gel, comprising reacting (A) a diamino-containing polysiloxane of the general formula: R, which may be the same or different, are selected from alkyl, aryl, olefin (vinyl), substituted or unsubstituted, or -OR9, wherein R9 is hydrogen or alkyl; R1 may be the same or different and may be selected from R, R2 or a diamino-containing radical of the formula -F1-NR5-F-NH2; with the proviso that at least one R1 group is a radical containing diamino; wherein F1 is linear or branched alkylene of 1-12 carbon atoms; F is linear or branched alkylene of 1-10 carbon atoms and R5 is hydrogen or lower alkyl; R2 may be the same or different and are selected from alkyl, aryl and olefin (vinyl), substituted or unsubstituted, or -OR9, wherein R9 is hydrogen or alkyl; R3 and R4, which may be the same or different, are selected from alkyl, aryl, protected or unprotected polyoxyalkylene, alkarylene, aralkylene or alkenyl, substituted or unsubstituted; a is an integer from 0 to 10,000; and b is an integer from 10 to 1000; with the proviso that when a pendant R1 group is a radical containing diamino, a may be 0 or a and b are present in the ratio of a: b of at least 1: 1 to 200: 1; with (B), a reactant containing acid selected from itaconic acid and / or trialkylsilyl ester derivatives thereof; substituted or unsubstituted cyclic acid anhydride; substituted or unsubstituted conjugated olefinic acid and mixtures thereof, at an elevated temperature in the presence of (C) a low molecular weight silicone oil or other solvent for a time sufficient to form an ionically crosslinked zwitterionic siloxane polymer of a similar consistency a thickened gel containing both carboxylic acid and secondary and / or tertiary amino radicals.

Description

Zwitterionic siloxane polymers and polymers ionically crosslinked formed therefrom.

Field of the Invention

This invention is directed to siloxane polymers zwitterionic and, more particularly, to siloxane polymers zwitterionic and aminofunctional polysiloxane polymers, modified, ionically crosslinked, of a consistency similar to gel, used to thicken silicone oils and other solvents. Crosslinks are polymer chain bonds in a network three-dimensional Ionic crosslinks are preferred because The viscosity of the final gel may also depend on the temperature and ionic intensity, thereby allowing it to produce additional post-processing.

Background of the invention

A variety of silanes and polymers of siloxane containing zwitterionic ions and it has been found that the use of some of them provides ionic crosslinking with the formation of gels and solid siloxane rubbers. However, the siloxane polymers that have been described so far that form gels under ionic crosslinking require the use of particular reactants due to the difficulty and cost of make polymers that allow sufficient crosslinking to reach gels and solid rubbers.

For example, a type of zwitterionic ionomers Silicone elastomers are described in US Pat. No. 4,525,567, granted on June 25, 1985 to Campbell et al. The Zwitterionic ionomers described exhibiting ionic crosslinking and form gels or solid rubber are characterized by being ionomers zwitterionic based on sultones while, in contrast to they, the composition of the present invention are ionomers zwitterionic based on amic acid or Pyrrolidone-carboxy, sulfur free. There is a additional distinction between Campbell and other products and the present invention in which the reactions can be carried out in presence of silicone oils or other solvents preferred.

In US Pat. No. 3,956,353, granted on May 11, 1976 at Plueddemann, the product of reaction of an amino functional silane of an acid anhydride cyclic. However, these reactants are limited to amines. vinyl-benzyl-functional that differ from the amine functional groups of the reactants of the The present invention does not require such replacement. On the other hand, The products described in the patent are low weight monomers molecular which are aqueous coupling agent compositions or alcoholic, in contrast to thickening compositions described in the present invention.

In US Pat. No. 5,008,424, Halloran and others describe zwitterionic aminofunctional siloxanes based in the reaction product of an amino functional siloxane and a cyclic acid anhydride for use in polishing formulations. However, Halloran and others describe only weight fluids low to medium molecular and also do not mention zwitterionic fluids High molecular weight or solvent thickening properties thereof.

U.S. Pat. No. 5,654,362, Schulz and others, describes silicone oils and thickened solvents using crosslinked silicone elastomers, particularly the fluid reaction containing silicone hydride with an alpha, Platinum catalyzed omega-diene in the presence of low molecular weight silicone oil. The present invention differs in that a zwitterionically crosslinked system is formed through non-covalent junctions inter- and / or intra-molecular Schulz and others also require that the gel is mechanically forced under shear until a paste or powder when low molecular weight oil is added additional. Unlike Schulz and others, here invention, gel consistency is related in part to the temperature and silicone oils and solvents can be added additional with heating when dilution is required additional.

As such, the present invention provides new and unique advantages over the typical prior art for Thickened silicone oil formulations that will become apparent later here.

Brief summary of the invention

This invention relates to new compositions. of ionically crosslinked polysiloxane of a similar consistency thickened gel, prepared by reacting (A) a polysiloxane containing diamino of the general formula (Formula 1):

Formula 1

one

in the what:

R, which can be the same or different, is select from alkyl, aryl, olefin (vinyl), substituted or not substituted, or -OR 9, where R 9 is hydrogen or I rent;

R_ {1} can be the same or different and can be selected from R, R2 or a radical containing diamino of the formula -F 1 -NR 5 -F-NH 2, wherein F 1 is linear or branched alkylene of 1-12 carbon atoms; F is linear alkylene or branched from 2-10 carbon atoms and R 5 is hydrogen or lower alkyl; with the proviso that at least one group R1 is a radical containing diamino;

R2 may be the same or different and may be selected from alkyl, aryl and olefin (vinyl), substituted or unsubstituted, or -OR 9, where R 9 is hydrogen or I rent;

R 3 and R 4, which may be the same or different, they can be selected from alkyl, aryl, protected or unprotected polyoxyalkylene, alkaryl, aralkylene or alkenyl, substituted or unsubstituted;

a is an integer from 0 to 10,000; Y

b is an integer from 10 to 1000; with the condition that if the pendant group R_ {1} is a radical that contains diamino, a can be 0 or a and b are present in a ratio of a: b of at least 1: 1 to 200: 1;

with (B), an acid-containing reactant selected from itaconic acid and / or ester derivatives trialkylsilyl thereof; substituted cyclic acid anhydride or unsubstituted; conjugated olefinic acid substituted or not substituted such as acrylic acid or an ester thereof or acid vinyl phosphorus, and mixtures thereof, at an elevated temperature (preferably from 25 ° C to 150 ° C), to form a polymer of Ionically crosslinked zwitterionic siloxane of a consistency similar to thickened gel that contains both acid radicals carboxylic as secondary and / or tertiary amino. Optionally, the reaction is carried out in the presence of (C) a silicone oil low molecular weight or other solvent, which additionally includes new methods to thicken silicone or other oils solvents up to a consistency similar to gel.

The ionically siloxane compositions crosslinked of the invention comprise a component of the zwitterionic siloxane polymer composition (referred to herein hereinafter "ionomer") which is represented by the Formula  two:

Formula 2

two

in the what:

R, R 2, R 3, R 4, a and b are as previously defined here; Y

R 7, which may be the same or different, they can be selected from R, R2 or a group selected from the group (a), (b) or (c) later, provided that at least A group R_ {7} is selected from:

(a) a group containing pyrrolidone of the general structure represented by Formula 3 if itaconic acid or an ester thereof is reacted with the primary amine of the diamine group;

Formula 3

3

in the what:

R '5 is hydrogen, lower alkyl or a Formula 3a group, with the proviso that if more than one equivalent of itaconic acid or ester thereof to the mixture of reaction containing the composition of formula 1, R '5 can include a group of Formula 3a:

Formula 3a

4

in the what:

R 6 is H, M or trialkylsiloxy, where M is a cation; Y

F_ {1} and F are as previously defined here;

(b) a group of the general structure represented by Formula 4, if approximately one is used equivalent of a cyclic anhydride reactant;

Formula 4

5

in the what:

R 5 is hydrogen or lower alkyl;

R 8 is a branched or unbranched alkylene radical branched, substituted or unsubstituted, preferably radicals ethylene, propylene, ortho-phenylene or alkylene unsaturated, such as vinylidene; Y

F_ {1} and F are as previously defined here; Y

(c) a group of the general structure of Formula 5 if a conjugated olefinic acid is used:

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Formula 5

\uelm{N}{\uelm{\para}{R'' _{5} }}

--F--

\delm{N}{\delm{\para}{H}}

--R_{11}--Z--F_ {1} -

 \ uelm {N} {\ uelm {\ para} {R '' _ {}}} 

--F--

 \ delm {N} {\ delm {\ para} {H}} 

--R_ {11} - Z

in the what:

R '' 5 is hydrogen, lower alkyl or a Formula 5a group, with the proviso that if more than an equivalent of conjugated olefinic acid to the reaction mixture containing the formula 1, R '' 5 could include a group of Formula 5a,

Formula 5a

-R_ {11} --- Z

R 11 is ethylene or substituted ethylene;

Z is selected from -CO2H;

F, F_ {1} are as previously defined here.

The crosslinked polysiloxane compositions ionically of the invention comprise at least 5 percent in weight of a low molecular weight silicone oil or other solvent, preferably a volatile silicone oil, although non-volatile silicone oils and / or can also be used solvents that do not contain silicone.

In yet another aspect of the present invention, provides an alternative method to prepare polymers Zwitterionic silicones suitable for forming gels of ionically crosslinked polysiloxane by reacting (A) a fluid or a composition containing organosilicone hydride, which has one or more terminal or side hydrides on the chain of polysiloxane with (B) an alkenyl-containing pyrrolidone ester terminal represented by Formula 6, in which the link alkylene is interrupted by a secondary amino group or tertiary:

Formula 6

8

in the what:

R 5 is hydrogen or lower alkyl;

R 12 is a trialkylsilyl ester; Y

F_ {1} and F are as previously defined here;

(C) in the presence of a metal catalyst noble, preferably soluble platinum, at an elevated temperature (preferably between 65 ° C and 130 ° C) for sufficient time to react, preferably to react in a manner substantially complete, the hydride groups in the fluid or the silicone composition with the olefinic pyrrolidone ester; Y (D) optionally in the presence of a low weight silicone oil molecular, followed by hydrolyzing the ester or esters trialkyl to form the ionomer Zwitterionic

In an additional embodiment, the silicone gel ionically crosslinked can be mixed with silicone oils of low additional molecular weight or other solvents and / or cosmetic or other ingredients, optionally with heating to produce formulated products.

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These and other objects of the invention will be made. evident from a consideration of the following description detailed.

Description of preferred modalities

The crosslinked polysiloxane compositions ionically of a gel-like consistency they are prepared by forming ionic crosslinks between polysiloxanes (ionomers) zwitterionics containing amino and carboxyl in the presence of a linear or cyclic polysiloxane of low molecular weight. The compositions containing silicone ionomer can be diluted optionally with additional low molecular weight polysiloxane with heating. Suitable silicone compositions containing 5 to 95 percent by weight, preferably 5 to 25 percent by weight weight, of ionically crosslinked zwitterionic polysiloxanes and of 95 to 5 percent by weight, preferably 95 to 75 percent in weight, of other ingredients, particularly volatile silicones and non-volatile low molecular weight and other solvents such as described below here form uniform silicone gels with A wide range of viscosity. Silicone gels have excellent properties including clarity, thixotropy, dilution With shear, thermoplasticity and can extend smoothly on the skin. They can be applied in cosmetic and medical products As the base oil. Compositions containing ionomers Silicones of the present invention have the unique property of rubbing easily on the skin, providing substantivity and improved water resistance These materials are also ideal for use in solid cosmetics such as antiperspirants and deodorants as well as are suitable for use in applications that require increased durability and behavior of silicones Industrial

The new polysiloxane compositions ionically crosslinked of the invention can be prepared by making react (A) a polysiloxane containing protected or non-protected diamino protected from the general formula (Formula 1):

Formula 1

9

in the what:

R, which can be the same or different, is select alkyl, aryl, olefin (vinyl) substituted or not substituted or -OR 9, where R 9 is hydrogen or I rent;

R_ {1} can be the same or different and can be selected from R, R2 and a radical containing diamino of the formula -F 1 -NR 5 -F-NH 2; with the proviso that at least one R1 group is a radical containing diamino, where F 1 is linear alkylene or branched from 1-12 carbon atoms, preferably propylene and isobutylene; F is linear alkylene or branched 1-10 carbon atoms, preferably ethylene, and R 5 is hydrogen or alkyl lower;

R2 can be the same or different and can be selected from alkyl, aryl and olefin (vinyl) substituted or not substituted or -OR 9;

R 3 and R 4, which may be the same or different, are selected from alkyl, aryl, polyoxyalkylene protected or unprotected, alkylene, aralkylene or alkenylene substituted or unsubstituted;

a is an integer from 0 to 10,000; Y

b is an integer from 10 to 1000; with the condition that when a pendant R_ {1} group is a radical containing diamino, a can be 0 or a and b are present in the a: b ratio of at least 1: 1 to 200: 1, preferably 10: 1 a 100: 1, most preferably from 15: 1 to 25: 1

with (B), an acid-containing reactant such as itaconic acid and / or trialkylsilyl ester derivatives thereof, substituted or not substituted cyclic acid anhydrides substituted, or substituted or unsubstituted conjugated olefinic acid substituted, and mixtures thereof, at an elevated temperature, preferably from 25 ° C to 150 ° C, to form a polymer of Ionically crosslinked zwitterionic siloxane of a consistency similar to gel containing radicals both carboxylic acid and secondary and / or tertiary amino. The reaction is carried out in presence of a low molecular weight silicone oil or others solvents, and additionally comprises new methods for thickening silicone oils or other solvents to a consistency similar to gel.

The crosslinked polysiloxane compositions ionically of the invention comprise a polymer component of protected or unprotected zwitterionic siloxane of the invention, represented by Formula 2:

Formula 2

10

in the what:

R, R 2, R 3, R 4, R 9, a and b are as previously defined here; Y

R_ {7}, which may be the same or different, may be selected from R_ {1} or a group selected from (a), (b) or (c) later, with the proviso that at least one R7 group is select from:

(a) a group containing pyrrolidone of the general structure represented by Formula 3 if approximately an equivalent of itaconic acid or ester thereof is made react with the primary amine of the diamine group;

Formula 3

eleven

in the what:

R '5 is hydrogen, lower alkyl or a group represented by Formula 3a, with the proviso that if charge more than one equivalent of itaconic acid or ester thereof to the reaction mixture containing the formula 1, R '5 can Include a group represented by Formula 3a:

Formula 3a

12

in the what:

R 6 is H, M or trialkylsiloxy, where M is a cation such as an alkali metal salt, alkaline earth metal, ammonium or substituted ammonium; Y

F_ {1} and F are as previously defined here;

(b) a group of the general structure represented by Formula 4, if approximately one is used equivalent of a cyclic anhydride reactant;

Formula 4

13

in the what:

R 8 is a branched or unbranched alkylene radical branched, substituted or unsubstituted, preferably ethylene, propylene, ortho-phenylene or alkylene radicals unsaturated such as vinylidene;

R 5 is hydrogen or lower alkyl; Y

F_ {1} and F are as previously defined here; Y

(c) a group of the general structure of Formula 5 if approximately one equivalent of olefinic acid is used conjugate;

Formula 5

\uelm{N}{\uelm{\para}{R'' _{5} }}

--F--

\delm{N}{\delm{\para}{H}}

--R_{11}--Z-F_ {1} -

 \ uelm {N} {\ uelm {\ para} {R '' _ {}}} 

--F--

 \ delm {N} {\ delm {\ para} {H}} 

--R_ {11} - Z

in the what:

R '' 5 is hydrogen, lower alkyl or a group represented by Formula 5a, with the proviso that if loaded more than one equivalent of conjugated olefinic acid to the reaction mixture containing formula 1, R '' 5 could include a group represented by Formula 5a;

Formula 5a

-R_ {11} --- Z

in the what:

R 11 is ethylene or substituted ethylene;

Z is -CO 2 H; Y

F and F_ {1} are as previously defined here.

The new ionically crosslinked compositions of a gel-like consistency that contain a class protected or unprotected zwitterionic of polysiloxanes, surprisingly and unexpectedly, they can be easily prepared and directly by reacting compositions or fluids corresponding protected or unprotected silicones that have one or more functional diamine groups, each of which groups must contain a primary amine group, with amounts Stoichiometric approximate, preferably 0.8 to 1.2 equivalents of an acid containing reactant including acid  itaconic or its ester, substituted or not substituted cyclic acid anhydrides substituted and substituted or non-substituted conjugated olefinic acids substituted, or mixtures thereof, by functional diamine group, at an elevated temperature for long enough for substantially all the acid reactant, such as acid itaconic or its ester, react with the primary amine group functional. Preferably, the reaction is carried out in presence of a non-volatile silicone oil or other solvent. In general, 0.5 to 2.5, preferably 0.8 to 1.2, equivalent of acid reactant, such as itaconic acid or its ester, by functional primary amine group is reacted with the fluid silicone containing diamino functionality, in which, by example, substantially all itaconic acid and preferably the entire group or the primary amine functional groups are reacts and a polysiloxane composition is formed with at less a carboxyl functional group, such as a group or groups carboxyl functional containing pyrrolidone, and / or its ester or Salt.

The reaction can be carried out pure or in up to 95% by weight of an inert solvent such as oils linear or cyclic low molecular weight polysiliconics, a alcohol, a hydrocarbon solvent, a chlorinated hydrocarbon and similar, as desired, at elevated temperatures of 25 ° C to approximately 175 ° C, preferably from 40 ° C to 130 ° C, depending the most preferred temperatures of the reactant choice acid. The reaction proceeds easily and the reaction generally Complete of itaconic acid or its ester or other reactants acids described here with the primary amine functional groups available and that include, when applicable, cycling for forming a pyrrolidone group will occur in about 1 to 5 hours. Usual analytical techniques can be used for amine and acid indices as well as to control viscosity, the color and the evolution of water and / or alcohol to determine the termination of the reaction.

Functional Diaminic Silicone Fluids protected or unprotected suitable for use in accordance with the practice of the invention, which have one or more functional groups diamine that contain a primary amine group, and that can connect terminally, laterally or both terminally and laterally, as desired, through an alkylene bond to Silicon, are well known and commercially available, by example of Dow Corning General Electric Witco and Shin-Etsu Diaminic Silicone Fluids suitable functional examples are silicone fluids that have one or more functional groups protected by aminoalkylaminoalkylene, including, for example, fluids aminoethylaminopropyl-functional silicones, such such as Shin-Etsu KF 393, and silicone fluids aminoethylaminoisobutyl-functional, such as X2-8107 and Q2-8220 of Dow Corning. Suitable unprotected silicone fluids include fluids Alkoxy or hydroxy terminated silicones such as KF857 from Shin-Etsu and other silicone fluids aminoethylaminopropyl-functional terminals in methoxy Although the equivalent weight of the fluids or silicone compositions that can be used in the preparation of functional polysiloxanes containing carboxyl Zwitterionics of a gel-like consistency of the present invention is not critical, suitable compositions may have equivalent weights of 10,000 or even more, although preferred in general silicone fluids having equivalent weights of 500 to 5,000

As indicated, the polysiloxane component carboxy-functional zwitterionic containing Pyrrolidone of the composition of the present invention is prepared easily by reacting silicone fluids diamino-functional in which each of the Diamine groups must contain a primary amine with itaconic acid or its ester. Itaconic acid (methylene succinic acid) is a compound of the formula:

in which

R 10, which may be the same or different, they are hydrogen, lower alkyl (1-6 atoms of carbon) or trialkylsilyl.

The itaconic acid compound is available commercially from Rhone Poulenc and Pfizer Chemicals Division, while ester derivatives thereof are available from Morflex Inc., Greensboro, N.C. The compounds are produced by known fermentation techniques but also They know chemical synthesis methods.

As indicated, the compositions containing Zwitterionic polysiloxane of a gel-like consistency they are also prepared by reacting silicone compositions protected and unprotected corresponding that have one or more diamine functional groups containing a primary amine group, as described herein, with an acid anhydride reactant cyclic at an elevated temperature of 25 ° C to 120 ° C in the presence of volatile and nonvolatile silicones of low molecular weight or others solvents However, the reaction at temperatures above 75 ° C for prolonged periods of time may alter negatively the product if the acidic reaction product formed from the anhydride and the amine begins to cycle to the imida Cyclic acid anhydrides that are suitable for reaction with the compositions of formula 1 are selected from group consisting of succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, octenyl succinic anhydride, dodecenylsuccinic anhydride, octadecenylsuccinic anhydride, citricanoic anhydride, dodecylsuccinic anhydride, anhydride polyisobutylensuccinic and other cyclic anhydrides, the succinic anhydride the preferred material to use here.

Conjugated olefinic acids are also suitable for use as a reactant to prepare compositions containing zwitterionic polysiloxane by the reaction with protected and unprotected silicone compositions that have one or more diamine functional groups in the presence of low molecular weight volatile silicones or other solvents a high temperatures in accordance with the practice of the present invention and include unsaturated carboxylic acids such as Acrylic acid, methacrylic acid and crotonic acid.

In another aspect of the present invention, provides an alternative method to prepare polymers Zwitterionic silicones suitable for forming gels of ionically crosslinked polysiloxane by reacting a fluid or a composition containing organosilicone hydride, which has one or more terminal or side hydrides on the chain of polysiloxane, with a pyrrolidone ester containing alkenyl terminal represented by Formula 6, particularly the ester trialkylsilyl: where the alkylene bond is interrupted by a secondary or tertiary amino group, such as:

Formula 6

16

in the what

R 12 is a trialkylsilyl ester; Y

F, F_ {1} and R_ {5} are as defined previously here;

in the presence of a noble metal catalyst (Group VIII metal), preferably a platinum catalyst soluble, at an elevated temperature (preferably between 65 ° C and 130 ° C) for long enough to react, preferably react substantially completely, the hydride groups on the silicone fluid or composition with the olefinic pyrrolidone ester, optionally in the presence of a low molecular weight silicone oil, followed by hydrolyzing the ester or trialkylsilyl esters to form the ionomer Zwitterionic

The low molecular weight silicone oil suitable for use when preparing polysiloxane compositions ionically crosslinked of the present invention having a gel-like consistency is suitably a silicone oil volatile inert, although silicone oils can also not be used volatile and a variety of inert solvents that do not contain silicone.

The expression low weight silicone oil molecular aims to include (i) volatile linear methylsiloxanes and low molecular weight cyclic, (ii) alkyl- and volatile and non-volatile and cyclic aryl siloxanes low molecular weight, and (iii) linear functional siloxanes and Low molecular weight cyclic. However, the most preferred they are linear and cyclic volatile volatile methylsiloxanes (VMS) molecular.

VMS compounds correspond to the formula medium unit (CH 3) a SiO (4-a) / 2 in which "a" has an average value of two to three. The compounds contain siloxane units linked by bonds = S-O-Si =. Representative units they are "M" monofunctional units, (CH 3) 3 SiO 1/2, and difunctional units "D", (CH 3) 2 SiO. The difunctional units do not specifically formed by dimethylsiloxane are referred to as general units D '.

The presence of trifunctional units "T", CH_ {3} SiO_ {3/2}, results in the formation of linear or cyclic branched volatile methylsiloxanes. The presence of tetrafunctional units "Q", SiO_ {4/2}, gives as a result the formation of branched linear methylsiloxanes or cyclic

Linear VMS has the formula (CH 3) 3 SiO {(CH 3) 2 SiO} and Si (CH 3) 3. The value of "y" is 0-5. The cyclic VMS has the formula {(CH 3) 2 SiO z. The value of "z" It is 3-6. Preferably, these methylsiloxanes volatiles have boiling points less than approximately 250 ° C and viscosities of approximately 0.65-5.0 centistokes (mm2 / s).

\hbox{Me _{3} SiO(Me _{2} SiO) _{3} }

SiMe_{3}; tetradecametilhexasiloxano (MD_{4}M) con un punto de ebullición de 245ºC, una viscosidad de 2,63 mm^{2}/s y fórmula Me_{3}SiO(Me_{2}SiO)_{4}SiMe_{3}; y hexadecametilheptasiloxano (MD_{5}M) con un punto de ebullición de 270ºC, una viscosidad de 3,24 mm^{2}/s y fórmula Me_{3}SiO(Me_{2}SiO)_{5}SiMe_{3}.Representative linear volatile methylsiloxanes are hexamethyldisiloxane (MM) with a boiling point of 100 ° C, a viscosity of 0.65 mm 2 / s and formula Me 3 SiOSiMe 3; octamethyltrisiloxane (MDM) with a boiling point of 152 ° C, a viscosity of 1.04 mm 2 / s and formula Me 3 SiOMe 2 SiOSiMe 3; decamethyltetrasiloxane (MD 2 M) with a boiling point of 194 ° C, a viscosity of 1.53 mm 2 / s and formula Me 3 SiO (Me 2 SiO) 2 SiMe 3 ; dodecamethylpentasiloxane (MD 3 M) with a boiling point of 229 ° C, a viscosity of 2.06 mm 2 / s and formula

 {{Me3 SiO (Me2 SiO) 3 

SiMe_ {3}; tetradecamethylhexasiloxane (MD 4 M) with a boiling point of 245 ° C, a viscosity of 2.63 mm 2 / s and formula Me 3 SiO (Me 2 SiO) 4 SiMe 3 ; and hexadecamethylheptasiloxane (MD 5 M) with a boiling point of 270 ° C, a viscosity of 3.24 mm 2 / s and formula Me 3 SiO (Me 2 SiO) 5 SiMe 3 }

Representative cyclic volatile methylsiloxanes they are hexamethylcyclotrisiloxane (D3), a solid with a point of boiling at 134 ° C and formula {(Me2) SiO3; octamethylcyclotetrasiloxane (D4) with a boiling point of 176 ° C, a viscosity of 2.3 mm 2 / s and formula {(Me2) SiO4; decamethylcyclopentasiloxane (D5) with a boiling point of 210 ° C, a viscosity of 3.87 mm2 / s and formula {(Me2) SiO5; Y dodecamethylcyclohexasiloxane (D 6) with a boiling point of 245 ° C, a viscosity of 6.62 mm 2 / s and formula {(Me2) SiO6. Volatile Branched Methylsiloxanes representative are heptamethyl-3 - {(trimethylsilyl)} trisiloxane (M3T) with a boiling point of 192 ° C, a viscosity of 1.57 mm 2 / s and formula C 10 H 30 O 3 Si 4, hexamethyl- {3,3-bis- (trimethylsilyl) oxy} trisiloxane (M4Q) with a boiling point of 222 ° C, a viscosity of 2.86 mm 2 / s and formula C 12 H 36 O 4 Si 5; Y pentamethyl {(trimethylsilyl) oxy} cyclotrisiloxane (MD 3) with the formula C 8 H 24 D 4 Si 4.

As previously noted, the present procedure also includes using alkyl- and volatile and non-volatile linear aryl siloxanes and Low molecular weight cyclic. Linear polysiloxanes Representative are compounds of the formula R '3 SiO (R' 2 SiO) y SiR '3 and Representative cyclic polysiloxanes are compounds of the formula (R '2 SiO) z, wherein R' is an alkyl group of 1-20 carbon atoms or an aryl group such as phenyl. The value of "y" is 0-80, preferably 0-20. The value of "z" is 0-9, preferably 4-6. These polysiloxanes have viscosities generally in the range of 1-100 centistokes (mm2 / s).

Other low volatile non-volatile polysiloxanes Representative molecular have the general structure:

17

in the what

n has a value to provide polymers with a viscosity in the range of approximately 100-1,000 centistokes (mm2 / s);

R 'is as previously defined here; Y

R '2 is an aryl group such as phenyl. Typically, the value of n is approximately 80-375.

Illustrative polysiloxanes are polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane and polydiphenylsiloxane.

Low molecular weight functional polysiloxanes they can be represented by siloxane fluids acrylamido-functional siloxane fluids acrylate-functional siloxane fluids amido-functional, siloxane fluids amino-functional, siloxane fluids carbinol-functional siloxane fluids carboxyl-functional, siloxane fluids chloroalkyl-functional, siloxane fluids glycol-functional, fluid ketal-functional, siloxane fluids mercapto-functional, siloxane ester fluids methyl-functional, siloxane fluids perfluoro-functional and siloxanes silanol-functional.

The present invention is not limited to gels of ionically crosslinked polysiloxane that also contain only low molecular weight inert polysiloxanes. Other types of Compatible solvents can gel with silicone Zwitterionic Thus, a single solvent or a mixture of solvents

By solvent is meant (i) compounds organic, (ii) compounds containing a silicon atom, (iii) mixtures of organic compounds, (iv) mixtures of compounds that contain a silicon atom or (v) mixtures of organic compounds and compounds containing a silicon atom, used to scale industrial to dissolve, suspend or change properties physical of other materials.

In general, organic compounds are preferably aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, aldehydes, ketones, esters, ethers, glycols, ethers glycolic, alkyl halides or aromatic halides, inert. Representatives of some common organic solvents are alcohols such as methanol, ethanol, 1-propanol, cyclohexanol, benzyl alcohol, 2-octanol, ethylene glycol, propylene glycol and glycerol; Aliphatic hydrocarbons such as pentane, cyclohexane, heptane, VM&P solvent, isoparaffinic solvents and mineral alcohols; halides of alkyl such as chloroform, carbon tetrachloride, perchlorethylene, ethyl chloride and chlorobenzene; hydrocarbons aromatics such as benzene, toluene, ethylbenzene and xylene; esters such as ethyl acetate, isopropyl acetate, ethyl acetoacetate, amyl acetate, isobutyl isobutyrate and benzyl acetate; ethers such as ethyl ether, ether n-butyl, tetrahydrofuran and 1,4-dioxane; glycol ethers such as ether ethylene glycol monomethyl, monomethyl ether acetate ethylene glycol, ethylene glycol monobutyl ether and monophenyl ether of propylene glycol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol, methyl amyl ketone and diisobutyl ketone; oil hydrocarbons such as mineral oil, gasoline, naphtha, kerosene, diesel, heavy oil and crude oil; lubricating oils such as spindle oil and turbine oil; fatty oils such as corn oil, soybean oil, olive oil, rapeseed oil, cottonseed oil, sardine oil, herring oil and whale oil. "Other" organic solvents heterogeneous can also be used, such as acetonitrile, nitromethane, dimethylisorbide, dimethylformamide, oxide propylene, trioctyl phosphate, butyrolactone, furfural, oil pine, turpentine and m-creosol.

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They are also intended to cover by the term solvent volatile flavoring agents such as oil gaulteria, peppermint oil, spearmint oil, menthol, vanilla, cinnamon oil, clove oil, bay oil, aniseed oil, eucalyptus oil, thyme oil, cedar leaves, nutmeg oil, cassia oil, peanut, licorice, high fructose corn syrup, oils citrus fruits such as lemon, orange, lime and grapefruit, essences of fruits such as apple, pear, peach, grape, strawberry, raspberry, cherry, plum, pineapple and apricot, and other flavoring agents useful including aldehydes and esters such as acetate cinnamon, cinnamaldehyde, eugenyl formate, p-Methylanisol, acetaldehyde, benzaldehyde, aldehyde anisic, citral, pear, decanal, vanillin, tolylaldehyde, 2,6-dimethyloctanal and 2-ethylbutyraldehyde.

It is also intended that the term solvent include volatile fragrances such as natural products and perfume oils Some natural products and oils of Representative perfumes are ambergris, benzoin, algalia, clove, leaf oil, jasmine, mate, mimosa, moss, myrrh, iris, oil sandalwood and vetivert oil, chemicals aromatics such as amyl salicylate, amylcinamide aldehyde, benzyl acetate, citronellol, coumarin, geraniol, acetate isobornyl, abelmosco and terpinyl acetate; and the various scented oils from classic families such as the family of floral bouquet, the eastern family, the Cypriot family, the family woody, the citrus family, the canoe family, the family of skins, the spice family and the herbaceous family.

Typically, the procedure is carried out. using approximately a 1: 1 molar ratio of the primary amine in the polysiloxane containing diamino and (A) itaconic acid or its ester derivative or (B) cyclic acid anhydride or (C) acids conjugated olefins or mixtures thereof, preferably in presence of a volatile low molecular weight methylsiloxane. Useful materials can also be prepared by carrying out the procedure with an excess of polysiloxane containing diamino or the acid-containing reactant described here with the warning that the resulting product is a polymer that contains predominantly zwitterionic ions or containing ions mixed zwitterionics. A mixed zwitterionic ion is defined here as a polymer that contains zwitterionic moieties, but that has an excessive anionic or cationic final charge. For example, a 1: 2 molar ratio of the primary amine in the polysiloxane that contains diamino and (A) itaconic acid or its ester derivative and / or (C) conjugated olefinic acids will react to form materials useful since the secondary amine will become an amine tertiary, which will be cationic below the isoelectric point. Corresponding products of (A) and (C) will be zwitterionic ions mixed with a net anionic charge. Product viscosity resulting will be reduced from slightly to much compared to the of the corresponding 1: 1 ratio preparation. The rest of the Composition comprises low molecular weight silicone oil or another solvent in amounts generally within the range of approximately 5-95% by weight of the composition, preferably about 75-95% by weight.

Compositions containing silicone viscoelastic zwitterionics of the present invention have a particular value in formulations for personal care. Due to the unique volatility characteristics of the VMS component of these compositions can be used alone or combined with others cosmetic fluids, to form a variety of products for the Personal care without a prescription.

Thus, they are useful as carriers in antiperspirants and deodorants, as they leave a dry feeling and do not cool the skin during evaporation, lubricants and can be used to improve the properties of skin creams, skin care lotions, moisturizers, treatments facials, such as pain or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colonies, sacks, sunscreens, lotions before shaving and after shaving, liquid soaps, shower soaps and shower foams. They can also be used in hair shampoos, hair conditioners, hair sprays, emulsions, permanent, epilators and cuticle toppings, to improve the brightness and drying time and provide advantages and conditioning.

In cosmetics, they will work as agents dispersants, levelers and extension for pigments in makeup, color cosmetics, bases, blushes, pencils lips, lip balms, eye lines, masks, skin removers  oil, colored cosmetic removers, and powders. Are used as controlled contribution systems for soluble substances in oil and water such as vitamins, when incorporated into bars, gels, lotions, sprays and rotating balls, compositions impart a silky smooth cast. The present compositions that contain viscoelastic zwitterionic silicone have more uses beyond the area of personal care, including, for example, as a  charging or insulation material for electronic items, cable electric and RTV fluids, a barrier for stains or water for ground stabilization, as a substitute for materials epoxies in the electronics industry.

They are also useful as carriers for Crosslinked silicone rubber particles. In that application, (i) allows ease of incorporation of particles in phases silicone or organic such as shutters, paints, coatings, greases, adhesives, defoamers and compounds of encapsulated; and (ii) provide a modification of the rheological, physical or energy absorption properties of such phases in its pure or finished state.

In addition, the present compositions containing viscoelastic zwitterionic silicone are able to function as carriers for pharmaceuticals, biocides, herbicides, pesticides and other biologically active substances; and can be used to incorporate water and water soluble substances in hydrophobic systems Examples of some substances soluble in Water are salicylic acid, glycerol, enzymes and glycolic acid. By example, enzymes can be combined in the silicone gel and mix in intense detergent systems to prolong your duration of active storage. Other variations can be made in the compounds, compositions and methods described herein without depart from the essential features of the invention. The Forms of the invention are exemplary and not limitations of their scope defined in the claims.

The following examples illustrate the present invention in more detail.

Example 1

Preparation of a fluid diamino-functional protected by trimethylsilyl which It has an average composition of MS 376 D '15 M.

The following products are combined intermediate:

1) 280 g of DC 200 fluid, 1000cS

2) 30.96 g of aminoethylaminopropylmethyldiethoxysilane (D ')

3) 8.1 g of water

4) 1.6 g of KOH

The mixture is slowly heated to 160 ° C and volatile materials are removed during this period of heating. This temperature is maintained for 6 hours. To the cool, add 2 ml of glacial acetic acid and stir well in the reaction. The product is filtered leaving a viscous liquid transparent with the following characterization:

Alkali index, theory = 55.36

Alkali index, found = 58.7

Equivalent weight = 1911 g / eq.

Example 2 Zwitterionic Polymer

Product reaction of Example 1 (MD 376 D '15 M) and itaconic acid, 20% by weight den D_ {5}.

The following intermediate products are combined in a reaction vessel:

19.11 g of silicone fluid of Example 1

1.3 g of itaconic acid

82 g of decamethylcyclopentasiloxane (D5)

The mixture is slowly heated to 115 ° C with good stirring and maintained at 115 ° C until all are consumed the crystals of itaconic acid. There is a notable increase in viscosity during cooling. All the mix of reaction gelled but could be reversibly liquefied at heat additionally.

Example 3 Zwitterionic Polymer

Product reaction of Example 1 (MD 376 D '15 M) with dodecenylsuccinic anhydride.

The following intermediate products are combined in a reaction vessel:

19.11 g of silicone fluid of Example 1

2.66 g of dodecenyls succinic anhydride

87 g of decamethylcyclopentasiloxane (D_ {5})

Silicone fluid and anhydride represent together 20% by weight in D5. The mixture is heated until approximately 50-60 ° C. An increase of  considerable viscosity The temperature is maintained that way. for 1/2 hour and then allowed to cool. You get a transparent gel that would flow when reheating.

Example 4 Mixed Zwitterionic Polymer

Siloxane reaction with pendant diamino Dow Corning Q2-8220 (equivalent weight 3965) with two equivalents of acrylic acid (equivalent weight = 72) in D5 with 20% by weight non-volatile solids.

They are combined in a reaction vessel 39.65 g of Q2-8220, 1.44 g of acrylic acid and 164 g of Decamethylcyclopentasiloxane (D5). The mixture is stirred and heats to about 125-130 ° C and it Hold for about 4 hours. There is an increase in considerable viscosity in the reaction mixture upon cooling the mixture. The acid analysis of the mixture indicates the presence of only about 0.02% acrylic acid as opposed to the initial concentration of 0.7%.

Example 5 Mixed Zwitterionic Polymer

The siloxane reaction with pendant diamino Dow Corning Q2-8220 (equivalent weight 3965) with an equivalent of dodecyl succinic anhydride (DDSA) is added together with an amount of D5 sufficient to dilute the solids to  20% by weight. After the completion of the reaction, a equivalent of itaconic acid.

Equivalent weights of reactants

Q2-8220 of Dow Corning = 3965 (by amino pendant radical)

Dodecylsuccinic Anhydride = 266

Itaconic acid = 130

The reactants are combined in a container of reaction with a 0.01 molar base in a reaction vessel in the following proportions:

Q2-8220 = 39.65 g

DDSA = 2.66 g

Total solids of previous ingredients 43.61 g require 20% solids concentration in a batch weighing 218 g, requires 174.44 g of decamethylcyclopentasiloxane (D_ {5}).

Q2-8220, DDSA and D5 are combine (alkali index = 5.2) and heat to 60 ° C for 2 hours. Alkali index = 2.3.

This suggests a complete conversion because alkali index after the first phase should = index of acid;

\ frac {(0,01) (45100 \ meq \ of \ KOH)} {(216.7 g) *} = 2.58

* Since itaconic acid has not been added still, the total weight of 218-1.3 = 216.7. TO then 1.3 g of itaconic acid and the mixture of Reaction is maintained at 115 ° C for approximately 2 hours. When it cools, the product mixture is a transparent viscous gel. A final acid index is 4.9 compared to 5.17 theoretical.

Example 6 Zwitterionic Polymer

A mixture of 16.12 g of a fluid of polysiloxane diamino-?,? -functional available from Shin-Etsu under the trade name KF857, 1.3 g of itaconic acid and 52.3 g of D 5 is combined in a  reaction vessel and heated to 115-120 ° C for 2 hours. You get a product reaction which is a transparent viscous fluid that solidifies when cooling The reaction product has a solids content of 25% and an alkali index of 8.4 and an acid index of 8.2.

Example 7 Zwitterionic Polymer

Witco Silsoft® A-887 is a diamino pendant protected polysiloxane of a molecular weight quite low with an equivalent weight of 3624 g / mol. They were added 120.7 g of Silsoft A-887 to 375 g of DC-245 and were reacted with amounts of an equivalent or 4.3 g of itaconic acid for 2 hours at 125 ° C and It had a viscosity of 450 cP upon cooling. Reaction product it has a solids content of 25% and an alkali index of 4.2 and an acid index of 4.0.

Example 8 Mixed Zwitterionic Polymer

116.4 g of Silsoft are added A-887 to 375 g of DC-245 and are made react with two equivalents or 8.6 g of itaconic acid for 2 hours at 125 ° C. The reaction product has a viscosity of 200 cP on cooling. The reaction product has a content of 25% solids and an alkali index of 3.65 and an acid index of 8.61.

Example 9 Zwitterionic Polymer

241.4 g of Silsoft are added A-887 to 250 g of DC-245 and are made react with an amount of an equivalent or 8.6 g of acid Itaconic for 2 hours at 125 ° C. The reaction product has a viscosity above 100,000 centipoises upon cooling, a 50% solids content, an alkali index of 8.2 and an index of 7.9 acid.

Example 10 Pure zwitterionic polymer

Dow Corning net reaction Q2-8220 (described in Example 5) with a equivalent of itaconic acid.

96.8 g are combined in a reaction vessel of Q2-8220 and 3.2 g of itaconic acid. The mixture is stir and heat to about 125-130 ° C and it stays for about 2 hours. There is a considerable viscosity increase during the phase of heating. The cooled product is a hardened rubber transparent with a viscosity> 3.5 million centipoise, a  alkali index of 14.3 and an acid index of 16.7.

Example 11 Pure zwitterionic polymer

Dow Corning net reaction Q2-8220 with two equivalents of itaconic acid.

93.7 g are combined in a reaction vessel of Q2-8220 and 6.3 g of itaconic acid. The mixture is stir and heat to about 125-130 ° C and it stays for about 2 hours. There is a considerable viscosity increase during the phase of heating. The cooled product is a white gel with a viscosity 500500.00 centipoise, an alkali index of 8.9 and an acid index of 33.1. The comparison of example 10 with the Example 11 illustrates the viscosity increase characteristics optimal 1: 1 molar ratio of primary amine to reactant It contains acid.

Example 12 Zwitterionic Polymer

A mixture of 18 g (0.005 mol) of Shin-Etsu KF-874, 1.75 g of octadecenylsuccinic anhydride (ODSA) and 78.9 g of D5, which represents a 20% active solution, heated to 70 ° C for an hour. The final product is a transparent gel, which it has an alkali index of 2.3 (theoretical 2.8) and the index of acidity of 2.8. The final product was a transparent gel.

Example 13 Zwitterionic Polymer

A mixture of 18 g (0.005 mol) of KF-874, 1.5 g of dodecenylsuccinic anhydride (DDSA) and 78.4 g of D5, which represents an active solution to 20%, heated to 50 ° C for one hour. The alkali index of the product is 2.5 and the acid number of 2.7. The final product it is a transparent thickened fluid with a viscosity of 23,440 cP at 25 ° C

Example 14 Zwitterionic Polymer

A mixture of 18 g (0.005 mol) of Shin-Etsu KF-874, 1.75 g of octadecenylsuccinic anhydride (ODSA), 39.45 g of Isopar® M of Exxon and 39.45 g of D5, which represents an active solution at 20%, heated to 70 ° C for one hour. The alkali index of the reaction product is 2.9 and the acid number is 3.0. The Final product is a transparent gel.

Examples 15-20

A sedimentation study is carried out in 100 ml graduated cylinders to determine the intrinsic value of the present compositions for suspending or dispersing solids inorganic sunscreens, antiperspirants and pigments. The polymer system of the invention of Example 7 is used in the Preparation of the compositions of Examples 18, 19 and 20. The inorganic sunscreen powder is micronized TiO2 coated with alumina from Uniqema called Uniq® UV1. Antiperspirant powder It is REHEIS REACH® 701 SUF (100%) and the pigment is iron oxide PureOxy® Umber from Hilton Davis Co. The additional solvent was Dow Corning cyclomethicone DC245. The proportion of ingredients used and the test results are presented in Table 1, a  continuation.

TABLE 1

Example fifteen 16 17 18 19 twenty Uniq UV1 one - - one - - Mashed potatoes Oxy Umber - one - - one - REACH 701 SUF - - one - - one DC 245 99 99 99 89 89 89 Example of product 7     -     -    -   10   10    10 Total 100 100 100 100 100 100

Data of sedimentation Start nothing nothing nothing nothing nothing nothing 30 minutes 98 * nothing two* nothing nothing nothing one day complete nothing complete nothing nothing nothing one week - nothing - nothing nothing nothing * supernatant present (ml)

These data clearly show that <2.5% of This new polymer (on an active basis) is compatible with, or acts as a dispersing agent or primary suspension agent for, antiperspirant salts, TiO2 and iron oxide powders. Optionally, other powders may include, but are not limited, mica, ZnO and PTFE and derivatives thereof. Such systems can also employ one or more co-dispersants additional.

Example 21

An antiperspirant is formulated with a ionically crosslinked composition of the combined invention and three other ingredients shown in Table 2 below. The antiperspirant product exhibits a high degree of ability to extension, softness, little or no residue, and dryness, among its beneficial properties

TABLE 2

Amount of ingredient Estol 1543 (Emollient) 6 parts Example Product two 70 parts Active ingredient antiperspirant 2. 3 parts Fragrance 1 part

The composition is formed by mixing the materials with a rotating mixer at 65 ° C and cooling to form a thickened product.

In Table 2, the Estol 1543 emollient is octyl palmitate, an alcohol ester 2-ethylhexyl and palmitic acid available from Uniqema. The antiperspirant active ingredients are tetrachlorhydrex-gly from aluminum-zirconium (INCI name of the CTFA) in form of a superfine micronized powder. However, the formulation may contain other active ingredients of antiperspirant salts  such as aluminum dihydrochloride, sesquichlorohydrate aluminum, trichlorhydrex-Gly de aluminum-zirconium, Pentachlorhydrex-Gly from aluminum-zirconium u Octachlorhydrex-Gly de aluminum-zirconium

The formulated antiperspirants contain generally a maximum use level of active salt ingredient antiperspirant 20% by weight type of aluminum-zirconium and 25% by weight type of Aluminum hydrochloride on an anhydrous basis.

Oils can be used in the formulation emollients other than octyl palmitate, such as oil mineral, peanut oil, sesame oil, avocado oil, coconut oil, peanut butter, almond oil, Safflower oil, corn oil, cottonseed oil, castor oil, olive oil, jojoba oil, paraffin, cod liver oil, palm oil, oil soy, wheat germ oil, flaxseed oil, sunflower; fatty acid esters such as isopropyl myristate, isopropyl palmitate, isopropyl stearate, stearate butyl, cetyl stearate, diisopropyl adipate, oleate isodecyl, diisopropyl sebazate and lauryl lactate; acids fatty such as lauric, myristic, cetyl, palmitic acid, stearic, oleic, linoleic and behenic; fatty alcohols such as lauryl, myristyl, cetyl, stearyl alcohol, isostearyl, oleyl, ricinoleyl, erucyl and 2-octyldodecanol; lanolin and its derivatives, such such as lanolin, lanolin oil, lanolin wax, alcohols lanolin, lanolin fatty acids, isopropyl lanolate, ethoxylated lanolin and acetylated lanolin alcohols; and hydrocarbons such as petrolatum and squalane. Suitable fragrances for use in Example 21 may include any of the Natural products and perfume oils listed previously.

Optional ingredients may be used in conjunction with, or they can replace, the antiperspirant salt to make or a Cosmetic gel or cream. Optional ingredients include: silicone compounds such as those listed previously Similar; crosslinked gelled organopolysiloxanes such as dimethicone / vinyldimethicone cross polymers; ingredients antimicrobial assets such as cyclosan; insect repellents; antifungal agents; Sunscreens; vitamins; extracts from plants; self-tanning active ingredients such as dihydroxyacetone; alternative solvents such as dimethylisosorbide and particulate materials such as silica pyrolysis or clays.

Examples 22-25

It is surprisingly that the products of this invention are film formers with excellent adhesive properties towards keratin and other surfaces Natural and synthetic The use of the compositions of the invention as components of a hair fixer / conditioner more illustrated  forward, as a primary and secondary. The present invention includes, but is not limited to, examples of following fixers, including additionally those resins and additives known to the expert in the technique. The next two groups of fixing compositions are prepare and each applies to eight groups of brown hair bleached and permanent (International Hair Imports & Products) and allowed to harden for two hours. Formulations prepared in percentage by weight and test results Organoleptics are shown in Table 3, below.

TABLE 3

Example 22 Example 2. 3 Example 24 Example 25 Product of 20.0 (4 g of - 5.0 (1 g from - Example 2 ingredient active) active ingredient) DC 245® 80.0 100.0 - 5.0 Ethanol - - 91.5 91.5 Amphomer® - - 3.0 3.0 AMP-95® (Angus) - - 0.5 0.5 Evaluation No. of people No. of persons No. of people No. of persons for example 22 for example 23 for example 24 for the example 25 Brightness 8 0 7 one Firmness 7 0 4 4 Combed in dry 3 5 8 0 Antistatic 3 5 7 one Retention of curly 8 0 5 3

Example 22 illustrates the properties as primary fixer / conditioner of the invention compared to the cyclomethicone control, example 23, which does not act as a fixative. Brightness, firmness (fixation) and curl retention (80% of HR, 25 ° C) all are significantly improved. Additionally, hair braids treated with the composition of Example 22 they have a highly conditioned emollient touch after comb. A dry touch can also be obtained from a combination of fixing polymers and other additives available commercially Amphomer®, INCI name of a copolymer of National octylacrylamide / acrylates / butylaminoethyl methacrylate Starch and Chemical, is a zwitterionic fixative known in the technique for having excellent fixing properties and for being hard to dry combing when used alone. Surprisingly, the Example 24 is firmly the same as Example 25, but it is significantly improved in gloss properties, combing in dry and antistatic

Examples 26-28

Wet and similar cleaning towels and similar items are particularly useful for removing stains perianales and other spots of the skin. U.S. Pat. recent, such as US 5,863,663, 5,763,332 and 5,756,112 describe synthetic non-woven towels and a sheet of tissue paper that treats with a high aqueous phase inverse emulsion internal elaborated to break when rubbing. In particular, US 5,756,112, used an emulsifier of organopolysiloxane-polyalkylene, which established a water retention and aesthetic feel better than organic emulsifiers. This patent further describes organopolysiloxane-polyalkylene emulsifiers covalently crosslinked for this application.

Surprisingly, the interfacial tension of non-covalently crosslinked products of the present invention revealed that products of an equivalent weight less than 4000 g / mol began to significantly decrease activity interfacial between a cyclomethicone similar to an oily phase and Water. A significant interfacial activity of derivatives of lower equivalent weight suggests utility as co-emulsifier It is found that the activity Q2-5200 water-oil interfacial it is 4.75 dynes / cm at a concentration of 0.2% in D5. Without However, Q2-5200 is a mixture of dodecene, alkyl siloxane copolyols and solvents that makes a direct comparison with the present invention is difficult.

In Table 4, below, a specific illustration of the preparation of cleaning towels wet type according to the present invention treating sheets of tissue paper with inverse emulsions of high lipid water internal phase content.

TABLE 4

Example 26 Example 27 Example 28 Wax ceresin 6 6 6 (SP 252P melting point ~ 130 ° C) Arlacel® P135 two two two Span® 85 one one one Cyclomethicone D_ {5} - - one Example product 12 - one - Water deionized 84 84 84 NaCl 7 7 7 Test results Example 26 Example 27 Example 28 Stability of the emulsion 25ºC Stable Stable Stable Touch on dry Irregular Soft Irregular Shear required for High Medium Medium to break the emulsion

A liquid water emulsion is prepared to from the proportion of ingredients in the previous table using The following preparation: the aqueous phase is heated to 75 ° C. The remaining lipid phase ingredients (ceresin wax, D5 and polymer) are heated, with mixing, to a temperature of 75 ° C until melted. The aqueous phase is combined very slowly with the lipid phase and mixed under high shear with a flat blade agitator. The mixing is continue until the emulsion of lipid water is formed, as evidence for a rapid increase in viscosity above 2000 centipoise as measured with a Brookfield viscometer RV-Dv-II®. The emulsion can applied to a substrate according to the methods known by Those skilled in the art.

Example 29 Skin cream

The products of the invention are not soluble in water, but can be emulsified by traditional techniques as part of the oily phase in oil-in-water emulsions or Water in oil The requirement of the HLB of the oily phase is normally identifies through the use of standard mixtures of surfactants with known HLB values, for example using default combinations of SPAN® and TWEEN® from Uniqema, for find the most stable emulsion as shown in Table 5, to continuation.

TABLE 5

Formulation of skin cream (HLB 8) Example 29 Water deionized 78% Brij® 72 1.4 Brij 721 0.6 Product of Example 7 (25% of active ingredient) twenty

This emulsion passes the stability of the HLB 8 rating and is suitable for 15 minutes in a centrifuge at 5000 rpm. Those skilled in the art can modify This formula to include many functional attributes. One time emulsified and applied the substrate, the new polymer system It forms a continuous film on drying and provides emolliency, brightness and water resistance, among other attributes. For other part, a formulation sensitive active ingredient, including, but not limited to, vitamin C, could be incorporated first in the new polymer gel matrix and then emulsify by traditional methods to prolong the shelf life of the active ingredient.

Example 30 Shampoo

"Two in one" shampoos that include polydimethylsiloxanes, or derivatives thereof, and adjuvants of the Deposition have been marketed for more than a decade. The new silicone zwitterionic polymer system can be formulated in this kind of shampoo as illustrated in Table 6, a then, without difficulty, to provide additional post hardening and benefits thermally activated.

TABLE 6

Ingredients % in Weight DiWater 25.55 Celquat® SC-2401 (National Starch and Chemical Co) 0.30 Ammonium Lauryl Sulfate (28%) 30.00 Lauret-2-Sulfate ammonium (26%) 30.00 Example Product 7 2.00 Monasil PLN (Uniqema) 4.00 Estol® 3750 (Uniqema) 2.00 Alcohol cetearyl 1.00 Monamid® CMA3 (Uniqema) 3.00 Phospholipid® SV 4 (Uniqema) 1.20 Chloride cetrimony 0.75 Fragrance 0.20 Total 10.00 INCI names: 1 Polyquaternium-10, 2 Glycol Diestearate, 3 Cocamide-DEA, 4 Chloride-phosphate , from stearamidopropyl-PG-dimonium (y) Cetyl alcohol

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Celquat was slowly added to water SC-240 with high stirring speed while heated to 70 ° C. When the Celquat SC-240 is dissolve, add the ammonium lauryl sulfate and the Ammonium lauret sulfate with moderate agitation. Add the product of Example 7 to Monasil PLN, and then add to the game When the temperature reaches 70 ° C, add Estol 3750, cetearyl alcohol and Monamid CMA, add the Phospholipid SV and shake. Start cooling to 50 ° C and add cetrimony chloride below. Add the fragrance while cooling to room temperature.

The highly substantive formulation, example 30, is tested for damaged and permanent hair and is finds that it provides excellent wet hairstyle, increases the body (particularly after heat treatment using a conventional hot air gun) and leave the hair Bright and with a soft touch. Monasil® PLN acts as a Unique formulation adjuvant helping to emulsify silicones while decreasing the need for homogenization. Phospholipid SV works as a new deposition adjuvant silicone

Example 31 Waterproof coating

Color cosmetics, preparations of health and personal care, including, but not limited to, sunscreens, sunless sunscreens, eye lines, shadows of eyes, blushes, bases, toners, masks, preparations for the body or lips and dermal and transdermal patches, frequently lose effectiveness, run or stain in the presence of Water or simple mechanical abrasion. Industrial applications to Water proof may include, but are not limited to, adhesives, coatings, paints, fabrics, hard surface protection, corrosion protection, agricultural coatings, pesticides, insecticides, electronic materials and the like. It is desirable be able to formulate products so that such applications are water resistant, or more preferably waterproof, while also maintaining durability or resistance against nominal abrasive forces.

The waterproof property of the compositions of the invention on a keratin substrate are demonstrates using 10 cm x 10 cm (4 cm virgin wool) cuts inches x 4 inches) (overcast No. 526) obtained from Test Fabrics Inc, Middlesex NJ.

Two test clippings are cleaned first in isopropyl alcohol (IPA) to remove fatty stains residuals, such as lanolin, and then dry completely and their tare weights are recorded. Then one of the clippings, sample 31-a, are immersed in product of Sample 13 and removed. The other cutout shows 31-b, dipped only in cyclomethicone D5. Both cuts are dried at 45 degrees Celsius for 18 hours to ensure complete volatilization of cyclomethicone D_ {5}. Clipping weight is recorded at room temperature after the drying stage of 18 hours. The weight gain is presents in percentages on the weight of the untreated cutout: (31a) 2.3% and (31b) 0%.

A surfactant solution with 0.1% active ingredient is prepared using dioctyl sodium sulfosuccinate Monawet® MO-70R (from Uniqema). It is known in the art that this solution accelerates the wetting of tissues and other substances. A 0.5 ml aliquot of the wetting solution is applied to the center of each test cut and the times required for the wetting solution to visually "wet" the fabrics are as follows:
(31a)> 3 hours (water begins to evaporate from the cutout); (31b) 5 minutes. In conclusion, less than 2.3% polymer on an active ingredient base is required to completely waterproof a protein substrate such as keratin / wool. However, water proofing is applicable to other substances because water proofing is generally considered a property of the compositions of the present invention, since this property refers to increasing ionic crosslinking density during solvent evaporation. . This particular example is illustrative that new water proofing compositions and methods can be achieved by combining pendant zwitterionic grafts on α, \-alkoxy-functional polydimethylsiloxanes.

Example 32 Sunscreen

In Table 7, below, is an example of a water-in-oil emulsion that contains a sunscreen and the product of example 7, compared to a sample of control.

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TABLE 7

% Wt control Example 32% in weight Phase I Water deionized 81.8 81.8 Sulfate magnesium 0.7 0.7 Phase II Cyclomethicone D5 10.0 two Span 85 one one Example 7 (25% of polymer) 0 8 Arlacel P135 0.5 0.5 p-methoxycinnamate ethylhexyl 3 3 Stearate octyl 3 3

Emulsion procedure: Heat the water and MgSO 4 up to 75 ° C. Combine the oils (phase II) and heat to 85 ° C. Add water to oils very slowly With good agitation. Homogenize and cool. The products of Test are applied sparingly to glass plates and allowed to dry. Each plate is immersed in water for 20 minutes, extracted from the water for 20 minutes, put in water for 20 minutes, out of water for 20 minutes, for 80 minutes in total. The plates are let dry and then sprinkle with sim1 g of water deionized The plate treated with example 32, the polymer of the invention, it had water splashed to an extent greater than the Cyclomethicone control sample at the end of the test and so So much more water resistant.

The formulations for sun care water resistant containing the polymer system of the invention may also contain inorganic sunscreens, such as TiO2 or ZnO (available in powdered form or scattered) Inorganic filters can be used alone or in combination (i.e. combinations of TiO2 and ZnO) and also can be used together with organic sunscreens, in this or other emulsion or solution based formulations known to the experts in the art.

Example 33 Application to car wax

The durability of a uniform film is refers, in part, to the adhesion to a particular substrate, the intrinsic film toughness and environmental resistance general. Many wax preparations for commercial cars that contain silicones use mixtures of amino functional siloxanes such as SF 1705 and SF 1706 (GE Silicones, Waterford NY) for increase brightness intensity, ease of rubbing add / remove and add durability to attacks repeated environmental such as washing, rain and salts of the roads.

The exemplary test described in more detail further developed to track commercial waxes and experimental with respect to resistance to rain and car washes In particular, the exemplary washing test of car had to be rigorous enough for only one Commercial wax / polish will be able to pass more than one cycle.

Durability test (pass / fail)

Commercial product tested 5x water Alcojet® 1x Turtle Wax® Pass Failure Rain Dance® Pass Failure Rally® Pass Failure Zymol® Pass Pass* Black Magic Body Wet® Pass Failure Wildebeest Finish® Pass Failure Finish 2001® Failure Failure Mequiars® Pass Failure * also passed 3 cycles

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Test procedure

A rusty car hood is divided into panels 4 x 6 inch test. The honeycombs are washed with a solution 0.3% active sodium lauryl sulfate, rinsed and then then dry. Before the application of the wax, each panel is sprayed first with deionized water to ensure that the water does not form drops on the surface of the panel. The panels are dried and a test product is applied by rubbing each panel using a rag containing excess test product (1 g). The panels are air dried for 30 minutes, cleaned by polished for 1 minute and the entire application cycle is repeated one time. The initial brightness is determined as poor, moderate, good or excellent. The panels are then placed in a dishwasher Automatic domestic upside down and washed without detergent for 5 complete cycles The panels are removed when they are dry, they they put their treated faces face up on a table and they spray evenly with 1 gram of water. Test panels that formed raindrops evenly passed. Panels test that passed the 5 cycle water test are put back in the automatic dishwasher and wash 1 cycle using 70 g of Alcojet (low foaming powder detergent available from Alconox, Inc. NY, NY) and are reevaluated with respect to the formation of water drops. Those who passed a cycle could subsequently tested using additional wash cycles and evaluated.

Table 8, below, lists the proportion of ingredients used in the preparation of formulations Experimental wax for cars.

TABLE 8

Ingredients 33A control Control 33B Example 33A Example 33B amino control control carboxy Zwitterionic- Zwitterionic- functional functional functional from functional from the invention the invention GE SF 1705 (aminosiloxane) 3 - - - GE SF 1706 (aminosiloxane) 1.5 - - - Monasil PCA 100% from - 4,5 - - ingredient of active Example Product 14 - - 22.5 - Example Product 10 - - - 4,5 DC200 fluid (12,500 cSt) two two two two Carnauba Wax Nº 1 (Ross Wax) 6 6 two 6 Actinol® FA-2 (Arizona Chemical) 3 3 3 3 Isopar® H (Exxon) 24 24 6 24 Water 53 53 53 53 Kapolite SFS (Kapolite Inc.) 7 7 7 7 TORCH 0.5 0.5 0.5 0.5 Results Elimination by rubbing Good Limited Acceptable Good Intensity of brightness Good Good Good Excellent Water wash 5x Pass Pass Pass Pass Auto Alcojet Test 1x Failure Pass Pass Pass Auto Alcojet Test 3x Failure Failure Pass Pass

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The incorporation of acid siloxane commercial carboxylic-functional Monasil PCA (PCA dimethicone, Uniqema, Wilmington DE) instead of siloxanes GE aminofunctional (Control 33A) improved resistance to washed with Alcojet. However, only the formulations that contained the zwitterionic-functional polymers of the present invention (Example 33A and Example 33B) passed unexpectedly the 3 cycle test, illustrating new attributes of durability This particular example is relevant to low VOC applications since it uses only 6% of VOC's. As in the waterproofing example, Example 31, they are other substances are applicable because the durability is considers a general property of this invention as it refers to increase the density of ionic crosslinking during evaporation of the solvent.

Claims (13)

1. A method to prepare a composition ionically crosslinked of a gel-like consistency thickened, which comprises reacting (A) a polysiloxane containing diamino of the General Formula:  Formula 1 18 in the what: R, which can be the same or different, is select from alkyl, aryl, olefin (vinyl), substituted or not substituted, or -OR 9, where R 9 is hydrogen or I rent; R_ {1} can be the same or different and can be selected from R, R2 or a radical containing diamino of the formula -F 1 -NR 5 -F-NH 2; with the proviso that at least one R1 group is a radical containing diamino; wherein F 1 is linear alkylene or branched from 1-12 carbon atoms; F is linear or branched alkylene of 1-10 atoms of carbon and R 5 is hydrogen or lower alkyl; R2 can be the same or different and can be select from alkyl, aryl and olefin (vinyl), substituted or not substituted, or -OR 9, where R 9 is hydrogen or I rent; R 3 and R 4, which may be the same or different, are selected from alkyl, aryl, polyoxyalkylene protected or unprotected, alkarylene, aralkylene or alkenyl, substituted or unsubstituted; a is an integer from 0 to 10,000; Y b is an integer from 10 to 1000; with the condition that when a pendant R_ {1} group is a radical containing diamino, a can be 0 or a and b are present in the ratio of a: b of at least 1: 1 to 200: 1; with (B), an acid-containing reactant selected from itaconic acid and / or ester derivatives trialkylsilyl thereof; substituted cyclic acid anhydride or unsubstituted; conjugated olefinic acid substituted or not substituted and mixtures thereof, at an elevated temperature in presence of (C) a low molecular weight silicone oil or other solvent for a sufficient time to form a polymer of Ionically crosslinked zwitterionic siloxane of a consistency similar to thickened gel that contains both acid radicals carboxylic as secondary amino and / or tertiary. 2. The method of preparing a composition ionically crosslinked according to claim 1, in the that said acid-containing reactant is itaconic acid, the ester derivative of the trialkylsilyl radical of itaconic acid or mixtures thereof. 3. The method to prepare a composition ionically crosslinked according to claim 1, in the that said substituted cyclic acid anhydride reactant or unsubstituted is selected from the group consisting of anhydride succinic, maleic anhydride, phthalic anhydride, anhydride itaconic, octenyl succinic anhydride, anhydride dodecenyl succinic and anhydride octadecenyl succinic. 4. The method of preparing a composition ionically crosslinked according to claim 1, in the that said substituted or unsubstituted conjugated olefinic acid is an unsaturated carboxylic acid. 5. A crosslinked polysiloxane composition ionically comprising at least 5% by weight of an oil low molecular weight silicone or other solvent and a zwitterionic siloxane polymer composition comprising a component of the ionically crosslinked composition of a consistency similar to thickened gel, represented by the formula:  Formula 2 19 in the what: R, which can be the same or different, is select from alkyl, aryl, olefin (vinyl), substituted or not substituted, or -OR 9, where R 9 is hydrogen or I rent; R_ {1} can be the same or different and can be selected from R, R2 or a radical containing diamino of the formula -F 1 -NR 5 -F-NH 2; with the proviso that at least one R1 group is a radical containing diamino; wherein F 1 is linear alkylene or branched from 1-12 carbon atoms; F is linear or branched alkylene of 1-10 atoms of carbon and R 5 is hydrogen or lower alkyl; R2 can be the same or different and can be select from alkyl, aryl and olefin (vinyl), substituted or not substituted, or -OR 9, where R 9 is hydrogen or I rent; R 3 and R 4, which may be the same or different, are selected from alkyl, aryl, polyoxyalkylene protected or unprotected, alkarylene, aralkylene or alkenyl, substituted or unsubstituted; a is an integer from 0 to 10,000; Y b is an integer from 10 to 1000; with the condition that when a pendant R_ {1} group is a radical containing diamino, a can be 0 or a and b are present in the ratio of a: b of at least 1: 1 to 200: 1; R 7, which may be the same or different, will be select from R_ {1} or a group selected from (a), (b) or (c) later, with the proviso that at least one R7 group is select from: (a) a group containing pyrrolidone of the general structure represented by formula 3 if approximately an equivalent of itaconic acid or an ester thereof is made react with the primary amine of the diamine group;  Formula 3 twenty in the what: R '5 is hydrogen, lower alkyl or a group represented by Formula 3a, with the proviso that if loaded more than one equivalent of itaconic acid or ester thereof to the reaction mixture containing the composition of formula 1, R '5 may include a group represented by Formula 3a:  Formula 3a twenty-one in the what: R 6 is H, M or trialkylsiloxy, where M is a cation selected from an alkaline earth metal salt, metal alkali, ammonium or substituted ammonium; F1 is linear or branched alkylene of 1-12 carbon atoms; Y F is linear or branched alkylene of 1-12 carbon atoms; (b) a group of the general structure represented by Formula 4, if approximately one is used equivalent of a cyclic anhydride reactant;  Formula 4 22 in the what: R 8 is a branched or unbranched alkylene radical branched, substituted or unsubstituted; R 5 is hydrogen or lower alkyl; Y F_ {1} and F are as previously defined here; Y (c) a group of the general structure of Formula 5 if approximately one equivalent of olefinic acid is used conjugate:  Formula 5 -F_ {1} -

 \ uelm {N} {\ uelm {\ para} {R '' _ {}}} 

--F--

 \ delm {N} {\ delm {\ para} {H}} 

--R_ {11} - Z in the what: R '' 5 is hydrogen, lower alkyl or a group represented by Formula 5a, with the proviso that if loaded more than one equivalent of olefinic acid conjugated to the reaction mixture containing formula 1, R '' 5 is group represented by Formula 5a,  Formula 5a -R_ {11} --- Z in the what R 11 is ethylene or substituted ethylene; Z is -CO 2 H; Y F, F_ {1} are as previously defined here. 6. The crosslinked polysiloxane composition ionically according to claim 5, wherein the group R 7 of the composition represented by Formula 2 is select from R_ {1} or a group of (a), with the proviso that at less a group R_ {7} is a group of (a). 7. The crosslinked polysiloxane composition ionically according to claim 5, wherein at least a group R 7 is a group of (a) and in which R '' 5 is hydrogen or lower alkyl.

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8. The crosslinked polysiloxane composition ionically according to any one of claims 5 to 7, which comprises at least 5% by weight of a silicone oil of low molecular weight 9. The crosslinked polysiloxane composition ionically according to any one of the claims 5-8, in which the ratio of a: b is 15: 1 a 25: 1 10. The crosslinked polysiloxane composition ionically according to any one of the claims 5-9, comprising 95% to 75% by weight of a low molecular weight silicone oil or other solvent. 11. A cosmetic material selected from the group consisting of hair fixers, hair shampoos and Body lotions, creams and skin lotions, antiperspirants, deodorants, sunscreens, self tanners, preparations for lips, personal towels, skin patches or transdermal and color cosmetics comprising a composition of ionically crosslinked polysiloxane according to a any of claims 5 to 10. 12. A substrate coating material metallic and non-metallic, comprising the compositions of ionically crosslinked polysiloxane according to any one of claims 5 to 10. 13. The coating material for a substrate metallic and non-metallic according to claim 12, in the that said composition comprises the composition according to the claim 6.